CN114788058A - Method and apparatus for producing membrane/catalyst assembly - Google Patents
Method and apparatus for producing membrane/catalyst assembly Download PDFInfo
- Publication number
- CN114788058A CN114788058A CN202080086139.6A CN202080086139A CN114788058A CN 114788058 A CN114788058 A CN 114788058A CN 202080086139 A CN202080086139 A CN 202080086139A CN 114788058 A CN114788058 A CN 114788058A
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- China
- Prior art keywords
- electrolyte membrane
- membrane
- catalyst layer
- liquid
- catalyst
- Prior art date
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Images
Classifications
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- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- H01M2300/0082—Organic polymers
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Abstract
A method for producing a membrane-catalyst assembly in which a catalyst layer is joined to an electrolyte membrane, the method comprising: a liquid applying step of applying a liquid to only the surface of the electrolyte membrane before bonding in an atmospheric atmosphere; and a thermocompression bonding step of bonding the electrolyte membrane to which the liquid has been applied and the catalyst layer by thermocompression bonding. Provided is a production method which, when producing a membrane/catalyst assembly obtained by joining a polymer electrolyte membrane and a catalyst layer, can achieve both relaxation of thermocompression bonding conditions and improvement of adhesion between the catalyst layer and the electrolyte membrane with high productivity.
Description
Technical Field
The present invention relates to a method and an apparatus for producing a membrane-catalyst assembly, which is used in an electrochemical device such as a polymer electrolyte fuel cell and is formed by bonding a polymer electrolyte membrane and a catalyst layer.
Background
A fuel cell is a power generation device that obtains electric energy by electrochemically oxidizing a fuel such as hydrogen or methanol, and has recently attracted attention as a clean energy supply source. Among them, since the standard operating temperature of the polymer electrolyte fuel cell is as low as about 100 ℃ and the energy density is high, it is expected to be widely used as a small-scale distributed power generation facility and a power generation device for a mobile object such as an automobile or a ship. A polymer electrolyte membrane (hereinafter, may be simply referred to as an "electrolyte membrane") is a key material of a solid polymer electrolyte fuel cell, and in recent years, application to hydrogen infrastructure-related equipment such as a solid polymer electrolyte membrane water electrolysis device and an electrochemical hydrogen pump has been further studied.
When a polymer electrolyte membrane is applied to such an electrochemical device, a member in which the electrolyte membrane and a catalyst layer are joined is used. As examples of such a member, an electrolyte membrane with a catalyst layer in which a catalyst layer is formed on the surface of the electrolyte membrane is typical.
As a method for producing an electrolyte membrane with a catalyst layer, for example, the following method is known. First, a sheet of Polytetrafluoroethylene (PTFE) or the like having excellent releasability is used as a temporary substrate, and a catalyst solution is coated on the surface of the sheet. Then, the solvent in the coated catalyst solution is evaporated to form a dried catalyst layer. The dried catalyst layer and the electrolyte membrane were thermally pressed by using a surface press or a roll press, and the catalyst layer was transferred to the polymer electrolyte membrane. Finally, the temporary substrate is peeled from the catalyst layer transferred to the polymer electrolyte membrane. The reason why the method of transferring the catalyst layer to the electrolyte membrane after drying the catalyst layer as described above is employed is that if the solvent in the catalyst solution adheres to the electrolyte membrane, the electrolyte membrane swells and wrinkles are generated, and the shape thereof is deformed.
However, when the catalyst layer in a dry state is thermally pressed to the electrolyte membrane, adhesion between the catalyst layer and the electrolyte membrane may be insufficient unless high-temperature and high-pressure pressing is performed for a long time. On the other hand, if severe thermal compression bonding conditions are applied to improve the adhesion between the catalyst layer and the electrolyte membrane, the gas diffusion properties may be reduced by compressive deformation of the catalyst layer, making it difficult to obtain good power generation performance, or the durability may be reduced by damage to the electrolyte membrane due to thermal stress. On the other hand, simply lowering the temperature and pressure of the pressurization to reduce damage to the catalyst layer and the electrolyte membrane requires a corresponding increase in the pressurization time, and therefore the productivity is significantly reduced.
Therefore, various techniques have been proposed to achieve good adhesion between the electrolyte membrane and the catalyst layer while alleviating the thermocompression bonding conditions.
Documents of the prior art
Patent document
For example, the following methods are proposed: a method of bonding the catalyst solution to the electrolyte membrane while the catalyst layer has a slight solvent component left therein by semi-drying the catalyst solution as in patent document 1; a method in which a solution containing a proton-conductive binder resin is applied to the surface of a dried catalyst layer and the solution is joined to an electrolyte membrane before the solution is completely dried, as in patent document 2; as in patent document 3, a method of pressure bonding a laminate including an electrolyte membrane and a catalyst layer in a state of being immersed in a liquid is used.
Patent document 1: japanese patent No. 4240272 Specification
Patent document 2: japanese patent laid-open publication No. 2013-69535
Patent document 3: japanese patent laid-open publication No. 2009-140652
Disclosure of Invention
Problems to be solved by the invention
According to the method described in patent document 1, by leaving a solvent component in the catalyst layer to an extent that only the joint surface of the electrolyte membrane and the catalyst layer can be softened, the adhesion between the electrolyte membrane and the catalyst layer can be improved under mild thermocompression bonding conditions without causing wrinkles in the electrolyte membrane. However, drying control is difficult in which the solvent in the catalyst solution is partially removed by heating and the solvent remaining amount is made to be the same over the entire surface of the catalyst layer, and there is a problem that the interface resistance between the electrolyte membrane and the catalyst layer is large due to the difference in the dried state in the surface of the catalyst layer, and the quality is unstable because wrinkles are generated due to deformation of the electrolyte membrane and cracks are generated in the surface of the catalyst layer. Further, there is also a problem that the range of the solvent residual amount is narrow, leading to an increase in cost due to a decrease in productivity. Further, since the solvent composition of the catalyst solution is limited, it is difficult to flexibly cope with the variety change of the catalyst layer.
In addition, according to the method described in patent document 2, a solution of a binder resin having proton conductivity is applied to the surface of the catalyst layer that is to be joined to the electrolyte membrane, and the solution is joined before the solution is completely dried, whereby the solution functions as an adhesive, and the adhesion between the electrolyte membrane and the catalyst layer can be improved even at low temperatures and low pressures. However, since a solution of a binder resin having proton conductivity is used for joining the electrolyte membrane and the catalyst layer, the manufacturing cost is increased. Further, there are also the following problems: the binder resin is a component similar to the electrolyte membrane, and the thickness of the electrolyte membrane is substantially increased, which increases the resistance, and the organic solvent in the solution remains at the interface between the electrolyte membrane and the catalyst layer, which may cause a decrease in the power generation performance.
Further, according to the method described in patent document 3, in the pressure bonding step of pressure bonding the joined body including the electrolyte membrane and the joined body including the catalyst layer in a state of being immersed in a liquid, the electrolyte in the electrolyte membrane and the catalyst layer sufficiently absorbs the liquid, and is pressurized in a softened state, and enters the uneven portions of the joining surfaces of the catalyst layer and the gas diffusion layer to be joined, thereby obtaining strong joining properties, and the joining properties between the layers constituting the membrane/electrode joined body can be improved without increasing the temperature and pressure at the time of pressurization. However, since the entire member other than the interface relating to the joining is immersed in the liquid, it is difficult to suppress swelling of the electrolyte membrane and maintain the form. Further, since the deformation behavior of each member is different due to drying after the pressure bonding, there is a problem that it is difficult to obtain a uniform and flat joined body, and it is difficult to improve productivity by continuous processing using a long member in a roll shape.
The present invention addresses the problem of providing a production method that, when producing a member in which a polymer electrolyte membrane and a catalyst layer are joined together (hereinafter referred to as a "membrane/catalyst joined body"), can achieve both relaxation of thermocompression bonding conditions (pressure, pressure temperature, and pressure time) and improvement in adhesion between the catalyst layer and the electrolyte membrane with high productivity.
Means for solving the problems
In order to solve the above problems, the method for producing a membrane/catalyst assembly of the present invention has the following configuration. That is, a method for producing a membrane-catalyst assembly in which a catalyst layer is joined to an electrolyte membrane, the method comprising: a liquid applying step of applying a liquid to only the surface of the electrolyte membrane before bonding in an atmospheric atmosphere; and a thermocompression bonding step of bonding the electrolyte membrane to which the liquid has been applied and the catalyst layer by thermocompression bonding.
The apparatus for producing a membrane-catalyst assembly of the present invention has the following configuration. That is, the present invention provides an apparatus for producing a membrane-catalyst assembly in which a catalyst layer is joined to an electrolyte membrane, the apparatus comprising:
a liquid applying mechanism that applies a liquid to only the surface of the electrolyte membrane before bonding in an atmospheric atmosphere; and (c) and (d),
and a thermocompression bonding mechanism for bonding the electrolyte membrane to which the liquid has been applied and the catalyst layer by thermocompression bonding.
In the method for producing a membrane-catalyst assembly according to the present invention, the electrolyte membrane before joining preferably has a support on a surface different from a surface to which a liquid is applied.
In the method for producing a membrane-catalyst assembly according to the present invention, the liquid applied in the liquid applying step is preferably a liquid containing water.
In the method for producing a membrane-catalyst assembly according to the present invention, the water content in the water-containing liquid is preferably 90 mass% or more and 100 mass% or less.
In the method for producing a membrane-catalyst assembly according to the present invention, the liquid applied in the liquid applying step is preferably pure water.
In the method for producing a membrane-catalyst assembly according to the present invention, it is preferable that the liquid is applied only to the surface of the electrolyte membrane in the form of droplets in the liquid applying step.
In the method for producing a membrane-catalyst assembly according to the present invention, it is preferable that the liquid is applied by a sprayer in the liquid applying step.
In the method for producing a membrane/catalyst assembly according to the present invention, it is preferable that in the liquid applying step, the amount of the liquid in the thermocompression bonding step is per 1cm2The electrolyte membrane surface of (2) is 0.1. mu.L to 5. mu.L.
In the method for producing a membrane-catalyst assembly according to the present invention, a hydrocarbon-based electrolyte membrane is preferably used as the electrolyte membrane.
The method for producing a membrane-catalyst assembly according to the present invention preferably includes joining a catalyst layer to a surface of the electrolyte membrane by any of the above-described methods.
In the method for producing a membrane-catalyst assembly according to the present invention, it is preferable that the catalyst layer is supported by a substrate having gas permeability before being joined to the electrolyte membrane.
The method for producing a membrane-catalyst assembly of the present invention preferably includes: a step of forming a 1 st catalyst layer by applying a catalyst solution to one surface of an electrolyte membrane and drying the applied catalyst solution; and a step of forming a 2 nd catalyst layer by bonding a catalyst to the other surface of the electrolyte membrane by any of the above methods.
The method of producing a membrane-catalyst assembly according to the present invention preferably further comprises a step of coating the 1 st catalyst layer with a coating film, and the step of forming the 2 nd catalyst layer is preferably performed in a state where the 1 st catalyst layer is coated with the coating film.
In the apparatus for producing a membrane-catalyst assembly according to the present invention, the liquid applying means preferably applies the liquid in the form of droplets only to the surface of the electrolyte membrane.
In the apparatus for producing a membrane-catalyst assembly according to the present invention, the liquid applying means is preferably a sprayer.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a membrane/catalyst layer composite body can be produced with high productivity while simultaneously achieving relaxation of thermocompression bonding conditions (pressing pressure, pressing temperature, and pressing time) and improvement of adhesion between the catalyst layer and the electrolyte membrane.
Drawings
FIG. 1 is a side view schematically showing the configuration of a first embodiment of the apparatus for producing a membrane-catalyst assembly according to the present invention.
FIG. 2 is a side view schematically showing the structure of a second embodiment of the apparatus for producing a membrane-catalyst assembly according to the present invention.
Fig. 3 is a side view schematically showing the structure for forming a first catalyst layer in a third embodiment of the apparatus for producing a membrane-catalyst assembly according to the present invention.
FIG. 4 is a side view schematically showing the structure for forming a second catalyst layer in the third embodiment of the apparatus for producing a membrane-catalyst assembly according to the present invention.
Fig. 5 is a side view schematically showing the structure for forming a first catalyst layer in the fourth embodiment of the apparatus for producing a membrane-catalyst assembly according to the present invention.
FIG. 6 is a side view schematically showing the structure for forming a second catalyst layer in the fourth embodiment of the apparatus for producing a membrane-catalyst assembly according to the present invention.
FIG. 7 is a side view schematically showing the constitution for explaining the method of separating a temporary substrate in the first embodiment of the apparatus for producing a membrane-catalyst assembly according to the present invention.
FIG. 8 is a side view showing a schematic configuration of a heat insulating plate for explaining the first embodiment of the apparatus for producing a membrane-catalyst assembly according to the present invention.
Detailed Description
Although the present invention is not limited at all, the following effects can be considered as the effects of the present invention. In the thermocompression bonding step, the electrolyte membrane and the catalyst layer are pressed with a liquid applied to the joint surface of the catalyst layer and the electrolyte membrane, and air present at the interface is expelled and a state in which almost only the liquid is present between the electrolyte membrane and the catalyst layer is obtained. In this state, the liquid is evaporated by further applying heat, and the interface is vacuumed, so that the adhesion between the catalyst layer and the electrolyte membrane is improved. Further, the liquid is pushed into the electrolyte membrane by the pressure and permeates, whereby the electrolyte membrane is softened, and the adhesion between the two is further improved. Since the electrolyte membrane is held by the nip pressure at the time of thermocompression bonding immediately after the liquid permeation, the occurrence of swelling can be prevented. The liquid evaporated at the interface is discharged to the outside of the membrane/catalyst assembly through the pores of the catalyst layer having a porous structure.
The term "membrane-catalyst assembly" as used herein refers to not only an electrolyte membrane with a catalyst layer formed on the surface of the electrolyte membrane but also any laminate having a joint surface between the electrolyte membrane and the catalyst layer. For example, a membrane-electrode assembly in which a catalyst layer is formed on one surface of a substrate made of a gas-permeable carbon paper or the like, so-called a gas diffusion electrode, and an electrolyte membrane are joined together is also one aspect of the "membrane-catalyst assembly". Further, the operation of bonding a catalyst layer (only a catalyst layer, a gas diffusion electrode, or the like) to one surface of an electrolyte membrane from the other surface thereof from the state where the catalyst layer has already been formed on one surface of the electrolyte membrane is also included in the "production of a membrane-catalyst bonded body". As a method for forming the catalyst layer on one surface of the electrolyte membrane, for example, a method of directly coating the catalyst layer or a method of transferring the catalyst layer by using a catalyst layer transfer sheet can be used.
[ electrolyte Membrane ]
The electrolyte membrane to be used in the method and apparatus for producing a membrane-catalyst assembly according to the present invention is not particularly limited as long as it has proton conductivity and is capable of operating as an electrolyte membrane used in a polymer electrolyte fuel cell, a polymer electrolyte membrane type water electrolysis apparatus, an electrochemical hydrogen pump, and the like, and known or commercially available electrolyte membranes can be used. As such an electrolyte membrane, a polymer electrolyte membrane is preferable, and for example, a fluorine-based electrolyte membrane formed of perfluorosulfonic acid or a hydrocarbon-based electrolyte membrane formed of a hydrocarbon-based polymer having proton conductivity to a hydrocarbon-based skeleton can be used.
In particular, since hydrocarbon-based electrolyte membranes have a higher glass transition temperature and a larger shrinkage strain during heating than fluorine-based electrolyte membranes, it is often difficult to find transfer conditions having excellent productivity in a general thermocompression bonding method, and the production method and production apparatus of the present invention can be suitably applied.
As the electrolyte membrane, a composite electrolyte membrane obtained by combining a polymer electrolyte and a porous substrate may be used.
[ composite electrolyte Membrane ]
The composite electrolyte membrane is a membrane obtained by compositing a polymer electrolyte and a porous substrate, and is obtained by, for example, filling (impregnating) the porous substrate with the polymer electrolyte. Examples of the porous substrate include a hydrocarbon-based porous substrate containing a hydrocarbon-based polymer compound as a main component, a fluorine-based porous substrate containing a fluorine-based polymer compound as a main component, and the like.
Examples of the hydrocarbon-based polymer compound include Polyethylene (PE), polypropylene (PP), Polystyrene (PS), polyacrylate, polymethacrylate, polyvinyl chloride (PVC), polyvinylidene chloride (PVdC), polyester, Polycarbonate (PC), Polysulfone (PSU), Polyether Sulfone (PEs), polyphenylene oxide (PPO), polyarylene ether-based polymer, Polyphenylene Sulfide (PPs), polyphenylene sulfide sulfone, polyphenylene sulfide (PPP), polyarylene-based polymer, polyarylene ketone, polyether ketone (PEK), polyarylene phosphine oxide, polyether phosphine oxide, Polybenzoxazole (PBO), Polybenzothiazole (PBT), Polybenzimidazole (PBI), Polyamide (PA), Polyimide (PI), Polyetherimide (PEI), and Polyimide Sulfone (PIs).
Examples of the fluorine-based polymer compound include Polytetrafluoroethylene (PTFE), polyhexafluoropropylene, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVdF), Polychlorotrifluoroethylene (PCTFE), Perfluoroalkoxy Fluororesin (PFA), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and the like.
From the viewpoint of water resistance, chemical resistance, and mechanical properties, PE, PP, PPs, PEK, PBI, PTFE, polyhexafluoropropylene, FEP, and PFA are preferable, PTFE, polyhexafluoropropylene, FEP, and PFA are more preferable from the viewpoint of chemical resistance and chemical durability, and PTFE is particularly preferable because it has higher mechanical strength in the molecular orientation.
The composite electrolyte membrane is particularly preferably a membrane obtained by compositing a hydrocarbon electrolyte and a fluorine porous substrate. In this case, when the composite is formed, the nonionic fluorine-based surfactant is added to the hydrocarbon-based electrolyte solution, so that the hydrocarbon-based electrolyte can be easily filled (impregnated) into the fluorine-based porous substrate without a gap and with high efficiency.
The composite electrolyte membrane can be produced, for example, by impregnating a porous substrate with a polymer electrolyte solution and then drying the impregnated substrate to remove a solvent contained in the polymer electrolyte solution. The impregnation method may be as follows.
(1) A method of controlling the film thickness by removing the remaining solution while lifting up the porous substrate immersed in the polymer electrolyte solution,
(2) Method for coating porous substrate with polyelectrolyte solution by casting,
(3) A method of impregnating a porous base material with a polymer electrolyte solution cast and coated on a support base material.
[ catalyst layer ]
The catalyst layer to be supplied to the method and apparatus for producing a membrane-catalyst assembly according to the present invention is not particularly limited as long as it functions as a catalyst layer used in a polymer electrolyte fuel cell, a polymer electrolyte membrane type water electrolysis apparatus, an electrochemical hydrogen pump, or the like. In general, a catalyst layer having a porous structure formed of conductive particles such as carbon particles, catalyst particles such as platinum particles or platinum alloy particles supported on the conductive particles, and an electrolyte component such as an ionomer having proton conductivity can be used.
As an example, as the conductive particles, oil furnace black (oil flame black), gas furnace black (gas flame black), acetylene black, thermal black, carbon such as graphite, carbon nanotubes, graphene, and metal oxides such as tin oxide and titanium oxide can be preferably used. As the catalyst particles, a noble metal simple substance such as platinum, iridium, ruthenium, rhodium, palladium, or the like, an alloy with platinum such as manganese, iron, cobalt, nickel, copper, zinc, or the like, a 3-membered alloy with platinum or ruthenium, iridium oxide, or the like can be preferably used. As the electrolyte component, polysulfone sulfonic acid, polyaryletherketone sulfonic acid, polybenzimidazolesulfonic acid, polystyrenesulfonic acid, polyetheretherketone sulfonic acid, and polyphenylsulfonic acid of hydrocarbon polymers such as perfluorocarbonsulfonic acid polymers "Nafion" (registered trademark, manufactured by chemiurs), "Aquivion" (registered trademark, manufactured by Solvay corporation), "Flemion" (registered trademark, manufactured by asahi glass corporation), "Aciplex" (registered trademark, manufactured by asahi chemical corporation) and "Fumion" F (registered trademark, manufactured by Fuma-Tech) can be preferably used.
The catalyst solution is not particularly limited as long as the catalyst layer material is dispersed in a solvent that can be evaporated by drying and is sufficient to form a catalyst layer on the electrolyte membrane. In general, water, methanol, ethanol, alcohols such as 1-propanol, 2-propanol, t-butanol, and ethylene glycol, N-dimethylformamide, and N-methyl-2-pyrrolidone are preferably used as the solvent.
[ liquid applying step ]
The liquid applying step is a step of applying a liquid to the surface of the electrolyte membrane before joining, that is, the joining surface with the catalyst layer. The application of the liquid refers to a state in which the liquid is attached to the surface of the electrolyte membrane in an exposed state. In this case, the liquid is applied under an atmospheric atmosphere in order to minimize permeation of the liquid into the electrolyte membrane until the thermocompression bonding step. This is because a large amount of liquid permeating into the electrolyte membrane may swell and lose its shape.
In the liquid applying step, the liquid is applied only to the surface of the electrolyte membrane in the atmospheric atmosphere. By applying a liquid only to the surface of the electrolyte membrane, the process control parameters are reduced as compared with the case of applying a liquid to both the electrolyte membrane and the catalyst layer, and therefore, the following advantages are obtained: the manufacturing conditions are easy to be stable, and the liquid application amount of the joint surface is easy to be controlled and managed; and, the liquid amount unevenness in the bonding surface caused by the contact of the droplets before the thermocompression bonding step can be suppressed.
In addition, by applying the liquid in the atmospheric atmosphere, the liquid can be applied only to the surface of the electrolyte membrane, and the penetration of the liquid into the electrolyte membrane can be suppressed. By suppressing the permeation of the liquid into the electrolyte membrane, the shape variation of the electrolyte membrane can be suppressed. In addition, since the liquid permeating into the electrolyte membrane does not contribute to improvement of the adhesion of the interface but increases the energy consumption for evaporation, it is effective to suppress permeation of the liquid into the electrolyte membrane from the viewpoint of the production cost.
In the liquid application step, the electrolyte membrane is held by the support member on a surface of the electrolyte membrane different from the surface to which the liquid is applied, whereby swelling of the electrolyte membrane in the liquid application step can be further reduced. As such a support, a support used in the production of an electrolyte membrane or the like, which supports an electrolyte membrane in advance, and a support newly provided on a surface of the electrolyte membrane different from the surface to which a liquid is provided may be used, and a support newly provided through the catalyst layer from a state in which the catalyst layer is formed on one surface of the electrolyte membrane may be used as long as the production of the membrane/catalyst assembly in the present invention is not hindered, and the method for providing the support is not particularly limited. The material of the support is not particularly limited as long as it is a material formed of a combination of a plurality of materials such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate, Polycarbonate (PC), polyphenylene ether, polyether sulfone, polyarylate, polyether imide, polyamide imide, polyether ether ketone, polyphenylene sulfide (PPS), aromatic polyimide, and aromatic hydrocarbon polymer, a porous film using these materials, or a film formed of a combination of a plurality of materials such as an adhesive layer on one surface thereof, and the material is a material having a suitable thickness, flexibility, strength, and the like that contribute to good process passability in each process.
In the liquid applying step, the liquid is not particularly limited as long as it is evaporated by heating in the thermocompression bonding step as a subsequent step and is a material that is not toxic to the electrolyte membrane and the catalyst layer. For example, water, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol, and mixtures thereof can be used, and it is desirable to use a liquid containing at least water. Although wrinkles may be generated in the electrolyte membrane if the liquid undergoes a rapid temperature change during thermocompression bonding, the boiling point and specific heat of water are higher than those of the alcohol, and the temperature rise during thermocompression bonding is slow, so that if the liquid contains water, damage to the liquid can be suppressed. In addition, since water has lower permeability to the electrolyte membrane than alcohol, deformation of the electrolyte membrane shape due to permeation of liquid into the electrolyte membrane can be prevented. Further, the present invention can be implemented at low cost by using a liquid containing water, and also can make the environmental load on the manufacture small. Even when a liquid remains in the membrane/catalyst assembly joined by the production method and the production apparatus of the present invention, if the liquid is water, the performance of the apparatus using the membrane/catalyst assembly is not affected. The content ratio of water in the liquid containing water is more preferably 50 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 100% by mass. I.e. most preferably pure water is used as the liquid. Here, pure water is high-purity water containing no impurities, and means water at JIS K0557 (1998) a4 level obtained by a commercially available pure water production apparatus which collects water by passing through a reverse osmosis membrane and an ion exchange resin, or water having quality equivalent thereto.
The liquid may contain the solid component materials in a dissolved or dispersed state as long as the liquid has fluidity as a whole and the effects of the present invention can be obtained.
In the liquid application step, a method of applying a liquid is not particularly limited, and examples thereof include a method of forming a uniform coating film on the surface of the electrolyte membrane using a gravure coater, die coater, comma coater, or the like, and a method of applying a liquid in the form of droplets to the surface of the electrolyte membrane, and particularly preferably a method of applying a liquid in the form of droplets to the surface of the electrolyte membrane. The droplet shape here means a state where numerous droplets are present adhering to the surface of the electrolyte membrane. The droplets are collected by surface tension and have a size of 1cm on the electrolyte membrane2The following droplets. If the liquid is applied in the form of droplets, a minimum amount of liquid necessary for softening the electrolyte membrane can be uniformly applied to the joint surface. Need to make sure thatThe term "uniformity of the applied droplets" means that the droplets are applied to every 1cm2The total amount of liquid imparted to the interface is equal at any location. Even a liquid such as water which easily repels the electrolyte membrane and is difficult to form a uniform coating film can be easily applied in the form of droplets. Further, if the electrolyte membrane is in the form of droplets, the contact area with the electrolyte membrane is small, and therefore, permeation of the liquid into the electrolyte membrane until thermocompression bonding can be minimized. In addition, since the liquid droplets spread at the interface and are bonded to the surrounding liquid droplets by the nip pressure in the thermocompression bonding step, the electrolyte membrane can be softened on the entire interface.
In the liquid applying step, it is preferable that the amount of liquid at the time of starting the pressure bonding in the thermocompression bonding step is per 1cm2The electrolyte membrane surface of (2) is applied to the liquid in an amount of 0.1 to 5. mu.L. When the amount of liquid in the thermocompression bonding step is within the above-described preferred range, the electrolyte membrane can be sufficiently softened, the adhesion is sufficient, and the occurrence of a portion of the electrolyte membrane that is not softened due to partial non-bonding of liquid droplets at the time of the nip pressure in the thermocompression bonding step is avoided. The amount of liquid is more preferably 1cm per unit2The electrolyte membrane surface of (2) is 0.1. mu.L or more and 0.8. mu.L or less. The liquid amount can be measured as follows: a sample piece such as a PET film, the weight of which is measured, is stuck on the surface of an electrolyte membrane so as to be laminated on the electrolyte membrane, after a liquid is applied in a liquid applying step, the sample piece with the liquid is taken out immediately before the sample piece is brought into contact with a catalyst layer in a thermocompression bonding step to measure the weight thereof, and the weight per 1cm is calculated from the weight difference2Of the liquid. The size of the sample piece in this case may be a square with a side length of 1cm to 10 cm.
The smaller the average diameter of the droplets to be applied, the more preferable the droplets are, and more specifically, the droplets are preferably 300 μm or less in a state of adhering to the surface of the electrolyte membrane. Since the smaller the average diameter, the shorter the distance between the droplets can be made, the smaller the amount of liquid droplets can be bonded during the nip pressure in the thermocompression bonding step.
In the liquid applying step, as means for applying the liquid in the form of droplets, there are no particular limitations, and a method of spraying droplets by a nebulizer or ink jet, a method of condensing droplets on a bonding surface under a humidified atmosphere, a method of spraying a liquid atomized by an ultrasonic vibrator or the like, and the like can be used. The sprayer for spraying the liquid droplets is not particularly limited, and a two-fluid sprayer nozzle or the like for atomizing the liquid by atomizing the liquid with compressed air can be used.
When the above-described means for applying liquid in the form of droplets is used, it is preferable that the liquid applying means such as a spray nozzle be surrounded by a chamber in order to suppress scattering of the droplets to the surroundings. Further, although the pressure in the chamber may not be reduced, it is preferable to reduce the pressure slightly so that the pressure becomes negative with respect to the atmospheric pressure, since scattering of liquid droplets from a gap between the chamber and the electrolyte membrane to the surroundings can be suppressed.
[ thermocompression bonding Process ]
The electrolyte membrane subjected to the liquid applying step is then subjected to a thermocompression bonding step of thermocompression bonding with the catalyst layer. The thermocompression bonding step is a step of bonding the electrolyte membrane and the catalyst layer by heating and nipping the electrolyte membrane and the catalyst layer in a laminated state in which the liquid-applied surface of the electrolyte membrane is in contact with the catalyst layer.
The heating temperature in the thermocompression bonding step is not particularly limited, and is preferably not less than 220 ℃ and higher than the boiling point of the liquid to be applied to the electrolyte membrane (hereinafter referred to as "liquid boiling point"). The heating temperature is the highest reaching temperature at the joint surface between the electrolyte membrane and the catalyst layer in the thermocompression bonding step, and a thermocouple may be used for the measurement. When the heating temperature is within the above-described preferable range, the evaporation of the liquid does not take time, and the productivity is excellent, while the electrolyte membrane is not damaged by a hot band. The heating temperature in the thermocompression bonding step is more preferably 160 ℃ or higher than the boiling point of the liquid. The boiling point of the liquid is a boiling point at which the external pressure is one atmosphere, and in the case where the liquid to be evaporated has a single composition, the boiling point of the liquid is the boiling point of the liquid, and in the case where the liquid is a mixture, the boiling point of the monomer is the highest among the components of the mixture.
In the thermocompression bonding step, the pressure applied to the electrolyte membrane and the catalyst layer may be appropriately set, and is preferably 1MPa to 20 MPa. In the case where the pressure is within the above-described preferable range, the electrolyte membrane and the catalyst layer can be sufficiently adhered to each other, and on the other hand, since excessive pressure is not applied to the catalyst layer and the electrolyte membrane, the structure of the catalyst layer is not broken, mechanical damage to the electrolyte membrane is not increased, and durability and power generation performance are not deteriorated. The pressure in the thermocompression bonding step is more preferably 1MPa to 10 MPa.
The form of the nip in the thermocompression bonding step is not particularly limited, and may be a form in which the electrolyte membrane and the catalyst layer are in line contact in a single line like a heat press roll, or a form in which the electrolyte membrane and the catalyst layer are in surface contact with each other in a planar manner with a width in the transport direction like a double belt press mechanism.
[ production method based on roll-to-roll System ]
The method for producing the membrane-catalyst assembly of the present invention is preferably performed in a roll-to-roll manner. That is, the liquid applying step and the thermocompression bonding step are performed continuously in a roll-to-roll manner.
The roll-to-roll manufacturing method is, for example, the following manufacturing method: the electrolyte membrane in a long roll form and the catalyst layer in a long roll form (catalyst layer transfer sheet or gas diffusion electrode) are continuously unwound and conveyed, and a liquid application step and a heat pressure bonding step are performed to obtain a membrane/catalyst assembly.
The apparatus for producing a membrane-catalyst assembly described later is an example of a production apparatus capable of performing a roll-to-roll production method.
As is apparent from the above description and the description of the embodiments below, the present specification also discloses the following manufacturing apparatus for carrying out the manufacturing method.
(1) A device for producing a membrane-catalyst assembly in which a catalyst layer is joined to an electrolyte membrane, the device comprising: a liquid applying mechanism that applies a liquid to only the surface of the electrolyte membrane before bonding in an atmospheric atmosphere; and a thermocompression bonding mechanism that bonds the electrolyte membrane to which the liquid has been applied and the catalyst layer by thermocompression bonding;
(2) the apparatus for producing a membrane-catalyst assembly according to (1), wherein the liquid applying means applies the liquid in a droplet state only to the surface of the electrolyte membrane;
(3) the apparatus for producing a membrane-catalyst assembly according to (2), wherein the liquid applying means is a sprayer.
Hereinafter, specific embodiments of the present invention will be described with reference to schematic diagrams of manufacturing apparatuses for realizing the manufacturing method of the present invention. It should be noted that the following description is given for the purpose of facilitating understanding of the present invention, and the present invention is not limited to the above description, but those skilled in the art will readily understand that reference to preferred embodiments and modifications of the embodiments can be interpreted as a description of a manufacturing method or a manufacturing apparatus of the present invention as a general concept. In the present specification, for convenience, the upper side of each drawing is referred to as "upper" and the lower side is referred to as "lower", but the vertical direction of each drawing is not necessarily limited to the vertical direction with respect to the ground.
[ first embodiment: production of Membrane-catalyst Assembly (electrolyte Membrane with catalyst layer 1)
Fig. 1 is a side view showing a schematic configuration of an apparatus for producing an electrolyte membrane with a catalyst layer, which is one embodiment of the apparatus for producing a membrane-catalyst assembly according to the present invention.
In the membrane/catalyst assembly manufacturing apparatus 100 according to the present embodiment, the electrolyte membrane with a catalyst layer is manufactured as follows.
The electrolyte membrane 10 is unwound from the electrolyte membrane supply roll 11 and is supplied to the thermocompression bonding portion P via the guide roll 12. Catalyst layer transfer sheet supply rollers 21A, 21B are provided above and below the unwound electrolyte membrane 10, respectively. The catalyst layer joined to the upper surface of the electrolyte membrane 10 is formed using the catalyst layer transfer sheet 20A. The catalyst layer transfer sheet 20A is produced by, for example, previously applying a catalyst solution to a sheet to be a base material, and is unwound from the catalyst layer transfer sheet supply roll 21A with the base material supporting the catalyst layer, and is carried while carrying the base material side opposite to the catalyst layer forming surface in the order of the support roll 31A and the guide roll 22A. The substrate is also referred to as a temporary substrate because the substrate is peeled off after the catalyst layer and the electrolyte membrane are joined. The catalyst layer transfer sheet 20B for forming the catalyst layer formed on the lower surface of the electrolyte membrane 10 is unwound from the catalyst layer transfer sheet supply roller 21B, and is conveyed in the order of the support roller 31B and the guide roller 22B while carrying the base material side. By doing so, the catalyst layer transfer sheets 20A and 20B are supplied to the thermocompression bonding portion P so that the surfaces on which the catalyst layers are formed face the electrolyte membrane 10.
The material of the base material of the catalyst layer transfer sheets 20A and 20B is not particularly limited, and examples thereof include hydrocarbon-based plastic films typified by polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polyethylene (PE), polypropylene (PP), polyimide, polyphenylene sulfide, and the like, and fluorine-based films typified by Perfluoroalkoxyalkane (PFA), Polytetrafluoroethylene (PTFE), ethylene tetrafluoroethylene copolymer (ETFE), and the like.
More preferably, the base material has air permeability. The term "gas-permeable" means a gas-permeable property, and includes, for example, a case where pores communicating in the thickness direction of the substrate are present. By using a base material having gas permeability, vapor of liquid generated at the time of thermocompression bonding can be effectively discharged even in a state where the base material and the catalyst layer are bonded. As the substrate having air permeability, for example, a porous body formed of the above-described material can be used.
In order to remove wrinkles and slacks from the electrolyte membrane 10 and the catalyst layer transfer sheets 20A and 20B supplied to the thermocompression bonding portion P, the guide rollers 12, and 22A and 22B preferably use tenter rollers.
The apparatus 100 for producing a membrane-catalyst assembly according to the present embodiment is configured such that the catalyst layers are transferred to both surfaces of the electrolyte membrane 10, but may be configured such that the catalyst layers are transferred to only one surface of the electrolyte membrane 10.
In the present embodiment, a spray nozzle 30A is provided between the guide roller 12 and the thermocompression bonding portion P. The spray nozzle 30A has an ejection port facing the electrolyte membrane surface and is provided at a position spaced apart from the electrolyte membrane surface by a predetermined interval. Note that 1 or more spray nozzles 30A are provided in the width direction of the electrolyte membrane 10 depending on the width of the electrolyte membrane 10.
The spray nozzle 30A supplies water from a water supply tank, not shown, and sprays the supplied water from a spray port to apply droplets to the surface of the electrolyte membrane that is bonded to the catalyst layer.
Further, the sprayer nozzle 30A and a space S in which the droplets of the liquid supplied from the discharge port of the sprayer nozzle 30A to the electrolyte membrane fly are surrounded by the nozzle chamber 32A, and a decompression tank 34A for decompressing the space S is connected to the nozzle chamber 32A via a valve 33A for switching the decompression. The pressure reduction tank 34A slightly sucks outside air from the gap provided between the nozzle chamber 32A and the electrolyte membrane 10 by making the space S negative with respect to the ambient pressure of the manufacturing apparatus, thereby preventing the scattering of excess liquid droplets from the sprayer nozzle 30A to the surroundings. The water accumulated in the nozzle chamber 32A is discharged from a discharge pipe, not shown, provided in the nozzle chamber 32A, and returned to the water supply tank for reuse.
Note that, although the description of the liquid applying mechanism to the electrolyte membrane surface facing the catalyst layer transfer sheet 20A is given above, the description is omitted because the liquid applying mechanism (the spray nozzle 30B, the nozzle chamber 32B, the valve 33B, and the decompression tank 34B) to the electrolyte membrane surface facing the catalyst layer transfer sheet 20B has the same configuration.
The nozzle chambers 32A and 32B may not be depressurized, but are preferably depressurized to a small extent to prevent droplets from scattering around them. In this case, if the degree of decompression is too large, the amount of outside air sucked into the nozzle chambers 32A and 32B becomes large, and therefore the air flows in the nozzle chambers 32A and 32B may be disturbed, and the accuracy of applying droplets may be lowered. Therefore, the degree of decompression of the nozzle chambers 32A and 32B is suitably within a range of-50.0 kPa, preferably-10.0 kPa, and more preferably-5.0 kPa, with respect to the ambient pressure (atmospheric pressure) of the production apparatus, for example.
In this way, the electrolyte membrane 10 having the liquid applied to the joint surfaces of the catalyst layer transfer sheets 20A and 20B with the catalyst layer is supplied to the thermocompression bonding portion P and passes between the thermocompression rollers 40A and 40B. As shown in fig. 8, heat insulating plates 41A and 41B are preferably provided between the catalyst layer transfer sheet 20A and the heat press roll 40A, and between the catalyst layer transfer sheet 20B and the heat press roll 40B, respectively. By providing the heat insulating plates 41A, 41B, it is possible to prevent the liquid applied to the electrolyte membrane 10 from evaporating before the hot pressing due to the radiant heat emitted from the hot pressing rollers 40A, 40B.
The heat and pressure rollers 40A and 40B are connected to a drive mechanism, not shown, and can rotate while controlling the speed. The heat and pressure rollers 40A and 40B rotate at a constant speed while applying heat and pressure to the electrolyte membrane 10 and the catalyst layer transfer sheets 20A and 20B, thereby forming the membrane/catalyst layer assembly 13a by thermally pressing the catalyst layers to both surfaces of the electrolyte membrane 10 while conveying the electrolyte membrane 10 and the catalyst layer transfer sheets 20A and 20B in synchronization with each other in terms of the conveying speed. Note that, for the heat roller machines 40A and 40B, the heating device, the pressing device, and the like are not illustrated.
The material of the heat and pressure rollers 40A and 40B is not particularly limited, and it is preferable that one roller is a metal such as stainless steel, and the other roller is a structure in which a surface layer is covered with an elastomer such as a resin typified by rubber or an elastomer material. By using one of the heat and pressure rollers 40A, 40B as a metal, the electrolyte membrane and the catalyst layer can be sufficiently heated, and by using the surface layer of the other pressure roller as an elastic body, the pressure roller is flexibly deformed with respect to the catalyst layer transfer sheets 20A, 20B, and maintains good line contact, thereby enabling line pressure in the width direction of the base material to be uniform.
As the material of the elastomer, for example, when rubber is used, fluororubber, silicone rubber, EPDM (ethylene propylene diene rubber), chloroprene rubber, CSM (chlorosulfonated polyethylene rubber), urethane rubber, NBR (nitrile rubber), hard rubber, and the like can be used. The rubber hardness of the elastomer is preferably in the range of 70 to 97 DEG on the Shore A scale. When the rubber hardness of the elastomer is within the above-described preferred range, the amount of deformation of the elastomer is appropriate, the nip contact width with the catalyst layer transfer sheets 20A, 20B does not become excessively large, and the pressure necessary for bonding the electrolyte membrane 10 and the catalyst layer can be ensured, while the nip contact width does not become excessively small, and the nip time necessary for bonding can be ensured.
As the heating means of the heat and pressure rollers 40A and 40B, various heaters, steam, oil, and other heat mediums can be used, but are not particularly limited. The heating temperature may be the same temperature or different temperatures between the upper and lower rolls.
The method of controlling the nip pressure in the heat and pressure rollers 40A and 40B is not particularly limited, and the nip pressure may be controlled by using a pressing mechanism such as a hydraulic cylinder, or may be controlled by providing a gap with a constant interval between the heat and pressure rollers 40A and 40B by position control using a servo motor or the like, and controlling the nip pressure according to the size of the gap.
In the present embodiment, the thermocompression bonding section P uses the thermocompression rollers 40A and 40B as the line contact mechanism, but is not limited thereto. The mechanism may be a mechanism that nips the electrolyte membrane 10 and the catalyst layer transfer sheets 20A, 20B by a plurality of rollers in a plurality of line contacts, or may be a double belt press mechanism that nips by surface contact. When a plurality of sets of rollers are used, the number of rollers is not particularly limited, and preferably 2 to 10 sets.
In this way, the catalyst layers are transferred to both surfaces of the electrolyte membrane 10 through the thermocompression bonded portion P, thereby forming a membrane-catalyst assembly (catalyst layer-attached electrolyte membrane) 13 a.
Next, the temporary substrates 24A and 24B are peeled from the membrane/catalyst assembly 13a, which is an electrolyte membrane with a catalyst layer.
When the temporary substrates 24A and 24B are air-permeable substrates, the peeling method is not particularly limited. For example, the temporary substrates 24A and 24B can be peeled off by passing between the guide rollers 23A and 23B. Further, since the temporary substrate supports the electrolyte membrane via the catalyst layer while the temporary substrate is joined, an effect of preventing swelling of the electrolyte membrane can be obtained. Therefore, when it is difficult to evaporate almost the entire amount of the liquid only by the thermocompression bonding step, an additional drying step for drying the liquid may be provided between the time when the liquid passes through the thermocompression bonding section P and the time when the temporary base material is peeled. The additional drying step may also serve as the heating step. The drying temperature (hot air temperature, surface temperature of the heated roller) is suitably, for example, 120 to 250 ℃ and preferably 150 to 230 ℃. When the temporary substrates 24A and 24B are substrates having no air permeability, the temporary substrate 24A is preferably peeled off from the membrane/catalyst assembly 13a so as to be wrapped around the hot press roll 40A and the temporary substrate 24B is wrapped around the hot press roll 40B, as shown in fig. 7. The temporary base material is peeled off immediately after thermocompression bonding to expose the catalyst layer, so that vapor of the liquid generated in the thermocompression bonding step can be efficiently discharged.
The temporary substrate peeled from the membrane/catalyst layer bonded body 13A is wound around the temporary substrate winding rolls 25A and 25B via the guide rolls 23A and 23B, respectively. The membrane-catalyst bonded body 13a from which the temporary substrates 24A and 24B have been peeled is sent out by the sending-out roller 14 and wound into a roll by the winding roller 15.
The delivery roller 14 may be connected to a drive mechanism, not shown, and the electrolyte membrane 10 may be conveyed by controlling the speed of the press rollers 40A and 40B without nipping the electrolyte membrane 10 and the catalyst layer transfer sheets 20A and 20B.
[ second embodiment: production of Membrane-catalyst Assembly (Membrane-electrode Assembly)
Fig. 2 is a side view schematically showing the configuration of an apparatus for producing a membrane electrode assembly, which is one embodiment of the apparatus for producing a membrane/catalyst assembly according to the present invention.
In the membrane/catalyst assembly manufacturing apparatus 101 according to the embodiment shown in fig. 2, the membrane electrode assembly is manufactured as follows. Note that the same portions as those in the first embodiment will not be described.
In the second embodiment, gas diffusion electrodes 80A, 80B are supplied from gas diffusion electrode supply rolls 81A, 81B, instead of the catalyst layer transfer sheet used in the first embodiment. Gas diffusion electrode supply rollers 81A and 81B are provided above and below the unwound electrolyte membrane 10, respectively. The gas diffusion electrode 80A joined to the upper surface of the electrolyte membrane 10 is unwound from the gas diffusion electrode supply roll 81A, and is carried while carrying the gas diffusion electrode substrate side opposite to the catalyst layer formation surface in the order of the support roll 31A and the guide roll 22A. The gas diffusion electrode 80B joined to the lower surface of the electrolyte membrane 10 is unwound from the gas diffusion electrode supply roll 81B, and is carried while being carried on the gas diffusion electrode base material side opposite to the catalyst layer formation surface, in the order of the support roll 31B and the guide roll 22B. By doing so, the surfaces of the gas diffusion electrodes 80A and 80B on which the catalyst layers are formed are supplied to the thermocompression bonding portion P so as to face the electrolyte membrane 10.
The gas diffusion electrodes 80A and 80B and the electrolyte membrane 10 having a liquid applied to the bonding surfaces with the gas diffusion electrodes 80A and 80B are supplied to the thermocompression bonding portion P, pass between the thermocompression rollers 40A and 40B, and are bonded to form a membrane/catalyst bonded body (membrane/electrode bonded body) 13B. The membrane/catalyst assembly 13b as the membrane electrode assembly is fed out by a feed-out roll 14 and wound into a roll by a winding roll 15.
In the apparatus 101 for producing a membrane-catalyst assembly according to the present embodiment, the gas diffusion electrodes 80A and 80B are transferred to both surfaces of the electrolyte membrane 10, but the gas diffusion electrodes may be transferred to only one surface of the electrolyte membrane 10.
Here, the gas diffusion electrode is an electrode in which the above-described catalyst layer is laminated on an electrode base material. As the electrode substrate, an electrode substrate that operates as a gas diffusion electrode such as a polymer electrolyte fuel cell, a polymer electrolyte membrane type water electrolysis device, or an electrochemical hydrogen pump is used. Examples of the material include carbonaceous and electrically conductive inorganic substances, and more specifically, sintered products derived from polyacrylonitrile, sintered products derived from pitch, carbon materials such as graphite and expanded graphite, stainless steel, molybdenum, titanium, and the like. The form of these is not particularly limited, and for example, they may be used in a fibrous or particulate form, and from the viewpoint of fuel permeability, fibrous conductive materials (conductive fibers) such as carbon fibers are preferred. As the electrode substrate using the conductive fiber, any of woven cloth and nonwoven cloth may be used. The woven fabric may be, but not limited to, a plain weave, a twill weave, a satin weave, a grain weave (Japanese culture: binding) or the like. The nonwoven fabric may be one obtained by a papermaking method, a needle punching method, a spunbond method, a water jet (jet punch) method, a melt blowing method, or the like, without particular limitation. In addition, the knitted fabric may be used. Among the above fabrics, particularly when carbon fibers are used, the following can be preferably used: a woven fabric obtained by carbonizing or graphitizing a plain woven fabric using a flame-resistant spun yarn; a nonwoven fabric obtained by carbonizing or graphitizing a nonwoven fabric obtained by processing a flame-resistant yarn by a needle punching method, a spunlacing method or the like; and a nonwoven fabric felt obtained by a papermaking method using a flame-resistant yarn, a carbonized yarn, or a graphitized yarn. In particular, from the viewpoint of obtaining a thin and strong fabric, a nonwoven fabric or a cloth is preferably used. Examples of the carbon fibers used for the electrode substrate include Polyacrylonitrile (PAN) carbon fibers, phenol carbon fibers, pitch carbon fibers, rayon carbon fibers, and the like. As such an electrode substrate, for example, carbon paper TGP series, SO series, carbon cloth manufactured by E-TEK, Inc., manufactured by Toray corporation, etc. can be used.
In addition, the electrode base material may be subjected to: a hydrophobic treatment for preventing a decrease in gas diffusion and permeability due to water retention; a partially hydrophobic, hydrophilic treatment for forming a discharge path of water; carbon powder for reducing electrical resistance, platinum plating for imparting potential corrosion resistance, and the like. Further, a conductive intermediate layer containing at least an inorganic conductive substance and a hydrophobic polymer may be provided between the electrode substrate and the catalyst layer. In particular, when the electrode base material is a woven or nonwoven fabric of carbon fibers having a large porosity, the conductive intermediate layer can suppress the performance degradation caused by the catalyst solution penetrating into the gas diffusion layer.
[ third embodiment: production of Membrane-catalyst Assembly (electrolyte Membrane with catalyst layer) 3
In the third embodiment, first, the catalyst layer forming apparatus 102 shown in fig. 3 is used to form the 1 st catalyst layer on one surface of the electrolyte membrane. Formation of the 1 st catalyst layer was carried out as follows.
In the present embodiment, the electrolyte membrane 10' is supplied to the catalyst layer forming device 102 in a state of being supported on the support. The material of the electrolyte membrane support is not particularly limited, and for example, a PET film can be used.
The electrolyte membrane 10' with the support body is unwound from the electrolyte membrane supply roll 11, passes through the guide roll 12, and is supplied to the catalyst solution application mechanism 72. The catalyst solution application mechanism 72 is provided to face the electrolyte membrane 10' supported by the support roll 73. The catalyst solution coating means 72 supplies a catalyst solution from the catalyst solution tank 70 by using the catalyst solution feed pump 71, and forms a coating film by coating the supplied catalyst solution on the electrolyte membrane. The method of applying the catalyst solution in the catalyst solution applying mechanism 72 is not particularly limited. A gravure coater, die coater, comma coater, roll coater, spray coater, screen printing method, or the like can be applied.
In the present embodiment, the catalyst layer is formed by applying the catalyst solution to the electrolyte membrane 10 ', but the catalyst layer may be formed by transferring the catalyst layer to the electrolyte membrane 10' by using a catalyst layer transfer sheet.
Next, the drying mechanism 74 dries the coating film of the catalyst solution formed on the electrolyte membrane, and the solvent in the catalyst solution is evaporated to form the dried 1 st catalyst layer. The drying means 74 is not particularly limited as to the method of drying the catalyst solution. A method of conveying a heat medium such as hot air, a hot oven system using a heat heater, or the like can be used.
The membrane-1 st catalyst layer combined body 16 having the 1 st catalyst layer formed on the electrolyte membrane in this manner is fed out by the feed-out roller 14, and wound into a roll by the winding roller 17 with the support body.
Next, the 2 nd catalyst layer is formed on the back surface of the electrolyte membrane on the surface on which the 1 st catalyst layer is formed, using the membrane/catalyst assembly manufacturing apparatus 103 according to the embodiment shown in fig. 4. The formation of the 2 nd catalyst layer is carried out as follows.
The membrane-1 st catalyst layer bonded body 16 is unwound from the supply roll 18, passes through the guide roll 12, and further peels the support body 51 from the interface with the electrolyte membrane via the guide rolls 26A and 26B. At this time, the support 51 to be peeled is wound around the support winding roller 50.
The film-1 st catalyst layer bonded body 16 from which the support body 51 was peeled off was laminated on the 1 st catalyst layer surface via guide rollers 27A and 27B with the cover film 61 unwound from the cover film supply roller 60, and then supplied to the thermocompression bonding section P. The cover film 61 may be laminated before the support 51 is peeled.
The coating film 61 is used to protect the 1 st catalyst layer in the step of forming the 2 nd catalyst layer, and the material is not particularly limited as long as the function of the catalyst layer is not impaired by attachment and detachment. In general, sheets of natural fibers typified by paper and the like, hydrocarbon-based plastic films typified by polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polyethylene (PE), polypropylene (PP), polyimide, polyphenylene sulfide and the like, fluorine-based films typified by Perfluoroalkoxyalkane (PFA), Polytetrafluoroethylene (PTFE), ethylene tetrafluoroethylene copolymer (ETFE) and the like, or materials in which adhesiveness to an adherend is improved by providing these materials with an acrylic adhesive, a urethane acrylate adhesive, a rubber adhesive, a silicone adhesive and the like can be used. If the material is a material having improved adhesion, the electrolyte membrane can be supported while the electrolyte membrane is in contact with the liquid, and therefore, the effect of preventing swelling of the electrolyte membrane can be further obtained.
The film-1 st catalyst layer bonded body 16 supplied to the thermocompression bonding portion P is subjected to thermocompression bonding to form a film-catalyst bonded body (catalyst layer-attached electrolyte membrane) 13c in a state where the 1 st catalyst layer is covered with the cover film by the liquid applying step and the thermocompression bonding step similar to the first embodiment.
The membrane-catalyst bonded body 13c, which is the electrolyte membrane with the catalyst layer that has passed through the thermocompression bonded portion P, passes between the guide rollers 23A and 23B, and at this time, the temporary substrate 24A is peeled off from the membrane-catalyst layer bonded body 13c and wound by the temporary substrate winding roller 25A. The membrane-catalyst assembly 13c from which the temporary substrate 24A has been peeled is fed by the feed roller 14 and wound into a roll by the winding roller 15. The cover film 61 may be wound in a state of being bonded to the membrane/catalyst bonded body 13c, or may be peeled off from the membrane/catalyst bonded body 13c by the hot press roll 40B immediately after the pressing. By winding the cover film 61 in a state of being joined to the membrane/catalyst assembly 13c, it is possible to suppress wrinkles and elongation of the catalyst layer-attached electrolyte membrane and protect the catalyst layer from physical damage due to external factors. Further, by peeling the cover film 61 immediately after thermocompression bonding to expose the catalyst layer, vapor of the liquid generated in the thermocompression bonding step can be efficiently discharged. In this case, the catalyst layer may be protected with a new cover film before winding.
[ fourth embodiment: production of Membrane-catalyst Assembly (electrolyte Membrane with catalyst layer 4)
In the fourth embodiment, first, the 1 st catalyst layer is formed on one surface of the electrolyte membrane by the membrane-catalyst assembly manufacturing apparatus 104 according to the embodiment shown in fig. 5. The formation of the 1 st catalyst layer was carried out as follows.
In the present embodiment, the electrolyte membrane 10' is supplied to the catalyst layer forming device 104 in a state of being supported on the support. The electrolyte membrane 10' with the support body is unwound from the electrolyte membrane supply roll 11 and supplied to the thermocompression bonding portion P. The electrolyte membrane 10 'supplied to the thermocompression bonding portion P is thermocompression bonded with the 1 st catalyst layer by the liquid applying step and the thermocompression bonding step similar to the first embodiment, thereby forming a membrane-1 st catalyst layer bonded body 16'.
The film 1 st catalyst layer bonded body 16' is fed out by the feed-out roller 14 with the support and the temporary substrate of the catalyst layer transfer sheet 20A attached thereto, and wound up in a roll by the take-up roller 17.
Next, in the catalyst layer forming apparatus 105 according to the embodiment shown in fig. 6, the 2 nd catalyst layer is formed on the back surface of the electrolyte membrane on the surface on which the 1 st catalyst layer is formed. The formation of the 2 nd catalyst layer is carried out in the following manner.
The membrane-1 st catalyst layer bonded body 16' is unwound from the supply roll 18, and the support 51 is peeled from the interface with the electrolyte membrane via the guide rolls 26A and 26B. The support 51 peeled at this time is wound around the support winding roller 50.
The membrane-catalyst layer-1 bonded body 16' from which the support 51 has been peeled off is passed through the catalyst solution application means 72 and the drying means 74 as in the third embodiment to form a catalyst layer-2, thereby forming a membrane-catalyst bonded body (catalyst layer-attached electrolyte membrane) 13 d.
The membrane-catalyst assembly 13d, which is an electrolyte membrane with a catalyst layer, is fed out by a feed-out roll 14, and wound into a roll by a winding roll 15 in a state of being provided with a temporary substrate.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
In examples 1 to 6, as the catalyst layer transfer sheet, a catalyst layer transfer sheet roll was used, in which a catalyst coating liquid comprising a Pt-supported carbon catalyst TEC10E50E manufactured by Setarian metals industries, Ltd., and a "Nafion" (registered trademark) solution was applied to a continuous belt-shaped PTFE sheet as a base material, dried, and the thus-produced catalyst layer transfer sheet was rolled (base material width 100mm, thickness 8 μm) (platinum loading amount: 0.3 mg/cm)2)。
The electrolyte membranes of examples 2 to 6 were produced by the methods described in Japanese patent application laid-open No. 2018-60789.
[ example 1]
Using an apparatus having a schematic configuration shown in fig. 1, the catalyst layer was transferred from the catalyst layer transfer sheet to one surface of a commercially available "Nafion" (registered trademark) membrane used as an electrolyte membrane, which is a trade name NR211 (film thickness 25 μm), by the method described in the first embodiment.
In the liquid application step, 100% pure water was sprayed at a rate of 1cm using a fan-shaped spray nozzle CBIMV 80005S manufactured by IKEUCI2An amount of 0.5 μ L was given to the electrolyte membrane in the form of droplets.
In the thermocompression bonding step, a pair of thermocompression rollers having a diameter of 250mm was used, one of the rollers was a stainless steel roller, and the other was a fluororubber roller having a hardness of 90 ° (shore a). The pressure of the hot press roll was set to 3.0 MPa. The pressure is a measured value using a pressure measurement sheet (prescale) manufactured by fuji film (ltd). The roll surface temperature was 160 ℃ and the heating temperature was measured by a thermocouple provided at the joining interface, and the result was 115 ℃. The transfer speed of the electrolyte membrane and the catalyst layer transfer sheet was 4.0 m/min.
The obtained membrane/catalyst assembly was visually evaluated, and as a result, transfer failure of the catalyst layer, swelling of the electrolyte membrane, and wrinkles did not occur, and the membrane/catalyst assembly was high in quality.
[ example 2]
Using an apparatus having a schematic configuration shown in fig. 1, a catalyst layer was transferred from the same catalyst layer transfer sheet as used in example 1 to one surface of a polyether ketone polymer electrolyte membrane made of a polymer represented by the following formula (G1) by the method described in the first embodiment.
[ chemical formula 1]
In the liquid application step, a fan-shaped spray nozzle CBIMV 80005S manufactured by IKEUCI (R) was used to spray the electrolyte membrane at a rate of 1cm20.3. mu.L of 100% pure water was given.
In the thermocompression bonding step, a pair of thermocompression rollers having a diameter of 250mm was used, one of the rollers was a stainless steel roller, and the other was a fluororubber roller having a hardness of 90 ° (shore a). The pressure of the hot press roll was set to 4.5 MPa. The pressure is a value measured using a pressure measurement piece manufactured by fuji photo film (ltd). The temperature of the roll surface was 160 ℃ and the heating temperature was measured by a thermocouple provided at the joining interface, and was 115 ℃. The transport speed of the electrolyte membrane and the catalyst layer transfer sheet was 4.0 m/min.
The obtained membrane/catalyst assembly was visually evaluated, and as a result, transfer failure of the catalyst layer, swelling of the electrolyte membrane, and wrinkles did not occur, and the quality was high.
[ example 3]
Using an apparatus having a schematic configuration shown in fig. 1, the catalyst layer was transferred from the catalyst layer transfer sheet to one surface of the polyarylene polymer electrolyte membrane formed of a polymer represented by the following formula (G2) by the method described in the first embodiment.
[ chemical formula 2]
(in the formula (G2), k, m and n are integers, k is 25, m is 380, and n is 8.)
The liquid applying step and the thermocompression bonding step were performed in the same manner as in example 2.
The obtained membrane/catalyst assembly was visually evaluated, and as a result, transfer failure of the catalyst layer, swelling of the electrolyte membrane, and wrinkles did not occur, and the membrane/catalyst assembly was high in quality.
[ example 4]
Using an apparatus having a schematic configuration shown in fig. 1, the catalyst layer was transferred from the catalyst layer transfer sheet to one surface of the polyether sulfone polymer electrolyte membrane formed of the segment represented by the following formula (G3) and the segment represented by the following formula (G4) by the method described in the first embodiment.
[ chemical formula 3]
(in the formulae (G3) and (G4), p, q and r are integers, p is 170, q is 380 and r is 4.)
The liquid applying step and the thermocompression bonding step were performed in the same manner as in example 2.
The obtained membrane/catalyst assembly was visually evaluated, and as a result, transfer failure of the catalyst layer, swelling of the electrolyte membrane, and wrinkles did not occur, and the quality was high.
[ example 5]
An electrolyte membrane with a catalyst layer is manufactured by the method described in the third embodiment.
Using an apparatus having a schematic configuration shown in fig. 3, the catalyst solution was applied to one surface of a polyether ketone polymer electrolyte membrane made of a polymer represented by the above formula (G1), and dried to form the 1 st catalyst layer. The catalyst solution used was a catalyst coating solution composed of a Pt-supported carbon catalyst TEC10E50E manufactured by field noble metal industries, ltd, and a "Nafion" (registered trademark) solution. Drying was carried out at 120 ℃ for 5 minutes to obtain a catalyst layer having a layer thickness of 5 μm.
Next, using an apparatus having a schematic configuration shown in fig. 4, the catalyst layer 2 was transferred from the catalyst layer transfer sheet to the other surface of the polyether ketone polymer electrolyte membrane on which the catalyst layer 1 was formed, to form the catalyst layer 2. As the cover film laminated on the 1 st catalyst layer, "Lumiror" (registered trademark) of PET film manufactured by Toray corporation, having a film thickness of 75 μm, was used. The liquid applying step and the thermocompression bonding step were performed by the same method as in example 2.
The cover film was peeled off from the obtained electrolyte membrane with the catalyst layer, and as a result, no deposit or the like was observed on the cover film. In addition, the obtained electrolyte membrane with the catalyst layer was visually evaluated, and as a result, transfer failure of the catalyst layer, swelling of the electrolyte membrane, and wrinkles did not occur, and the quality was high.
[ example 6]
An electrolyte membrane with a catalyst layer is manufactured by the method described in the fourth embodiment.
The catalyst layer 1 was transferred from the catalyst layer transfer sheet to one surface of a polyether ketone polymer electrolyte membrane made of a polymer represented by the above formula (G1) by using an apparatus having a schematic configuration shown in fig. 5. The liquid applying step and the thermocompression bonding step were performed by the same method as in example 2.
Next, using an apparatus having a schematic configuration shown in fig. 6, the same catalyst solution as in example 5 was applied to the other surface of the electrolyte membrane on which the 1 st catalyst layer was formed, and dried to form the 2 nd catalyst layer.
The temporary substrate was peeled off from the resulting electrolyte membrane with the catalyst layer, and as a result, no adhering substance or the like was observed on the temporary substrate. In addition, the obtained electrolyte membrane with the catalyst layer was visually evaluated, and as a result, transfer failure of the catalyst layer, swelling of the electrolyte membrane, and wrinkles did not occur, and the quality was high.
[ example 7]
A membrane-catalyst assembly was produced in the same manner as in example 1, except that the following composite electrolyte membrane was used as the electrolyte membrane. The obtained membrane/catalyst assembly was visually evaluated, and as a result, transfer failure of the catalyst layer, swelling of the electrolyte membrane, and wrinkles did not occur, and the quality was high.
< composite electrolyte Membrane >
A composite electrolyte membrane was obtained by impregnating a PTFE porous substrate (registered trademark "Tetratex" manufactured by DONALDSON) having a thickness of 6 μm with the following fluorine-based electrolyte solution.
< fluorine-based electrolyte solution >
To 100 parts by mass of a 20% "Nafion (registered trademark)" n-propanol solution, 80 parts by mass of ethylene glycol was added, and the n-propanol was removed under reduced pressure to carry out solvent substitution, thereby obtaining an ethylene glycol solution of Nafion.
[ example 8]
A membrane-catalyst assembly was produced in the same manner as in example 5, except that the following composite electrolyte membrane was used as the electrolyte membrane. The obtained membrane/catalyst assembly was visually evaluated, and as a result, transfer failure of the catalyst layer, swelling of the electrolyte membrane, and wrinkles did not occur, and the membrane/catalyst assembly was high in quality.
< composite electrolyte Membrane >
A composite electrolyte membrane was obtained by impregnating a PTFE porous substrate (registered trademark "Tetratex" manufactured by DONALDSON) having a thickness of 6 μm with the following hydrocarbon electrolyte solution.
< Hydrocarbon-based electrolyte solution >
The polyether ketone polymer electrolyte represented by the above formula (G1) was dissolved in 100 parts by mass of an N-methylpyrrolidone (NMP) solution (electrolyte concentration: 13% by mass), and 0.26 part by mass of a nonionic fluorine surfactant (polyoxyethylene ether surfactant "FTX-218" manufactured by NEO corporation) was dissolved therein.
[ example 9]
A membrane-catalyst assembly was produced in the same manner as in example 1, except that the pressure in the nozzle chambers 32A and 32B was not reduced in the production apparatus of fig. 1. The obtained membrane/catalyst assembly was visually evaluated, and as a result, transfer failure of the catalyst layer, swelling of the electrolyte membrane, and wrinkles did not occur, and the membrane/catalyst assembly was high in quality.
Comparative example 1
Except that the liquid application step was not performed, in the same manner as in example 2, the catalyst layer was transferred from the same catalyst layer transfer sheet as used in example 1 described above to one surface of the electrolyte membrane, and the resulting membrane-catalyst assembly was visually evaluated, and as a result, transfer failure of the catalyst layer was observed.
Industrial applicability
The membrane-catalyst assembly of the present invention can be used as, for example, an electrolyte membrane with a catalyst layer or a membrane-electrode assembly, and is suitable for use in a polymer electrolyte fuel cell, a polymer electrolyte membrane-type water electrolysis device, an electrochemical hydrogen pump, and the like. When the membrane-catalyst assembly of the present invention is an electrolyte membrane with a catalyst layer, it is preferable to further laminate an electrode substrate and apply the membrane-catalyst assembly to the above-mentioned applications.
Description of the reference numerals
100. 101, 103, 104: apparatus for producing membrane/catalyst assembly
102. 105: catalyst layer forming apparatus
10. 10': electrolyte membrane
11. 18: electrolyte film supply roller
13a, 13b, 13c, 13 d: membrane/catalyst assembly
14: delivery roller
15. 17: winding roller
16. 16': Membrane-No. 1 catalyst layer laminate
12. 22A, 22B, 23A, 23B, 26A, 26B, 27A, 27B: guide roller
20A, 20B: catalyst layer transfer sheet
21A, 21B: catalyst layer transfer sheet supply roller
24A, 24B: temporary substrate
25A, 25B: temporary substrate winding roll
30A, 30B: spray nozzle
31A, 31B, 73: supporting roller
32A, 32B: nozzle chamber
33A, 33B: valve with a valve body
34A, 34B: pressure reducing tank
40A, 40B: hot-pressing roller
41A, 41B: heat insulation board
50: supporting body winding roller
51: support body
60: cover film supply roller
70: catalyst solution tank
71: catalyst solution liquid feeding pump
72: coating mechanism
74: drying mechanism
80A, 80B: gas diffusion electrode
81A, 81B: gas diffusion electrode supply roll
P: thermocompression bonding part
S: space(s)
Claims (16)
1. A method for producing a membrane-catalyst assembly in which a catalyst layer is joined to an electrolyte membrane, the method comprising:
a liquid applying step of applying a liquid to only the surface of the electrolyte membrane before bonding in an atmospheric atmosphere; and
and a thermocompression bonding step of bonding the electrolyte membrane to which the liquid has been applied and the catalyst layer by thermocompression bonding.
2. The method of producing a membrane-catalyst assembly according to claim 1, wherein the electrolyte membrane before joining has a support on a surface different from a surface to which a liquid is applied.
3. The method of producing a membrane-catalyst assembly according to claim 1 or 2, wherein the liquid applied in the liquid applying step is a liquid containing water.
4. The method of manufacturing a membrane-catalyst assembly according to claim 3, wherein a content ratio of water in the liquid containing water is 90% by mass or more and 100% by mass or less.
5. The method of manufacturing a membrane-catalyst assembly according to claim 4, wherein the liquid applied in the liquid applying step is pure water.
6. The method of producing a membrane-catalyst assembly according to any one of claims 1 to 5, wherein in the liquid applying step, the liquid is applied only to the surface of the electrolyte membrane in the form of droplets.
7. The method of producing a membrane-catalyst assembly according to claim 6, wherein in the liquid applying step, the liquid is applied by a sprayer.
8. The method of producing a membrane-catalyst assembly according to any one of claims 1 to 7, wherein in the liquid applying step, the amount of the liquid in the thermocompression bonding step is per 1cm2The electrolyte membrane surface of (2) is 0.1. mu.L to 5. mu.L.
9. The method for producing a membrane-catalyst assembly according to any one of claims 1 to 8, wherein a hydrocarbon-based electrolyte membrane is used as the electrolyte membrane.
10. A method for producing a membrane-catalyst assembly, comprising bonding a catalyst layer to the surface of the electrolyte membrane by the method according to any one of claims 1 to 9.
11. The method for producing a membrane-catalyst assembly according to any one of claims 1 to 10, wherein the catalyst layer is supported by a substrate having gas permeability before being joined to the electrolyte membrane.
12. A method for producing a membrane-catalyst assembly, comprising:
applying a catalyst solution to one surface of an electrolyte membrane and drying the catalyst solution to form a 1 st catalyst layer; and the combination of (a) and (b),
a step of forming a 2 nd catalyst layer by bonding a catalyst layer to the other surface of the electrolyte membrane by the method according to any one of claims 1 to 11.
13. The method of producing a membrane-catalyst assembly according to claim 12, further comprising a step of coating the 1 st catalyst layer with a coating film, and the step of forming the 2 nd catalyst layer is performed in a state where the 1 st catalyst layer is coated with the coating film.
14. An apparatus for producing a membrane-catalyst assembly in which a catalyst layer is joined to an electrolyte membrane, the apparatus comprising:
a liquid applying mechanism that applies a liquid to only the surface of the electrolyte membrane before bonding in an atmospheric atmosphere; and the combination of (a) and (b),
and a thermocompression bonding mechanism for bonding the electrolyte membrane to which the liquid has been applied and the catalyst layer by thermocompression bonding.
15. The apparatus for producing a membrane-catalyst assembly according to claim 14, wherein the liquid applying means applies the liquid in the form of droplets only to the surface of the electrolyte membrane.
16. The apparatus for producing a membrane-catalyst assembly according to claim 15, wherein the liquid applying means is a sprayer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019231591 | 2019-12-23 | ||
| JP2019-231591 | 2019-12-23 | ||
| PCT/JP2020/047640 WO2021132137A1 (en) | 2019-12-23 | 2020-12-21 | Manufacturing method and manufacturing device for film/catalyst assembly |
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| CN114788058A true CN114788058A (en) | 2022-07-22 |
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| CN202080086139.6A Pending CN114788058A (en) | 2019-12-23 | 2020-12-21 | Method and apparatus for producing membrane/catalyst assembly |
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|---|---|
| US (1) | US11929511B2 (en) |
| EP (1) | EP4084158A1 (en) |
| JP (1) | JPWO2021132137A1 (en) |
| KR (1) | KR20220119001A (en) |
| CN (1) | CN114788058A (en) |
| AU (1) | AU2020413859A1 (en) |
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| WO (1) | WO2021132137A1 (en) |
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| WO2023201353A2 (en) * | 2022-04-15 | 2023-10-19 | Twelve Benefit Corporation | Cox electrolyzer cell flow fields and gas diffusion layers |
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| JP4240272B2 (en) | 2002-05-14 | 2009-03-18 | トヨタ自動車株式会社 | Method for producing membrane-catalyst layer assembly |
| JP2009140652A (en) | 2007-12-04 | 2009-06-25 | Toyota Motor Corp | Membrane-electrode assembly manufacturing method |
| JP2013069535A (en) | 2011-09-22 | 2013-04-18 | Nitto Denko Corp | Manufacturing method of membrane electrode assembly for polymer electrolyte fuel cell |
| JP2018055945A (en) * | 2016-09-28 | 2018-04-05 | 三菱自動車工業株式会社 | Fuel cell stack |
| JP7087315B2 (en) | 2016-09-30 | 2022-06-21 | 東レ株式会社 | Polymer electrolyte composition and polymer electrolyte membrane using it, electrolyte membrane with catalyst layer, membrane electrode composite, polymer electrolyte fuel cell, electrochemical hydrogen pump and water electrolytic hydrogen generator |
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2020
- 2020-12-21 CA CA3163203A patent/CA3163203A1/en active Pending
- 2020-12-21 EP EP20904552.5A patent/EP4084158A1/en active Pending
- 2020-12-21 WO PCT/JP2020/047640 patent/WO2021132137A1/en unknown
- 2020-12-21 KR KR1020227014788A patent/KR20220119001A/en unknown
- 2020-12-21 CN CN202080086139.6A patent/CN114788058A/en active Pending
- 2020-12-21 AU AU2020413859A patent/AU2020413859A1/en active Pending
- 2020-12-21 US US17/785,530 patent/US11929511B2/en active Active
- 2020-12-21 JP JP2021512598A patent/JPWO2021132137A1/ja active Pending
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| JP2002289207A (en) * | 2001-03-26 | 2002-10-04 | Matsushita Electric Ind Co Ltd | Manufacturing method for hydrogen ion conductive polymer membrane with catalyst layer for fuel cell |
| US20040163760A1 (en) * | 2003-02-20 | 2004-08-26 | Jsr Corporation And Honda Motor Co., Ltd. | Manufacturing process for membrane-electrode assemblies |
| JP2005158518A (en) * | 2003-11-26 | 2005-06-16 | Jsr Corp | Manufacturing method of junction of electrolyte membrane and electrode |
| US20050173061A1 (en) * | 2004-02-09 | 2005-08-11 | Aisin Seiki Kabushiki Kaisha | Method for manufacturing membrane electrode assembly |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP4084158A1 (en) | 2022-11-02 |
| CA3163203A1 (en) | 2021-07-01 |
| WO2021132137A1 (en) | 2021-07-01 |
| KR20220119001A (en) | 2022-08-26 |
| AU2020413859A1 (en) | 2022-08-11 |
| US11929511B2 (en) | 2024-03-12 |
| US20230058120A1 (en) | 2023-02-23 |
| JPWO2021132137A1 (en) | 2021-07-01 |
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